The present invention relates to novel azeotropic compositions, a process for the production of foams in which these azeotropic compositions are used and to foams produced using these azeotropic compositions.
The use of trichloromonofluoromethane (CFC-11) and other chlorofluorocarbons as blowing agents in the production of urethane foams is well known. These CFC blowing agents are also known to have an adverse effect upon the ozone layer in the atmosphere. The urethane foam industry is therefore investigating methods for producing foams with good physical properties without using CFC blowing agents.
Initially, the most promising alternatives appeared to be hydrogen-containing chlorofluorocarbons (HCFCs). U.S. Pat. No. 4,076,644 for example, discloses the use of 1,1-dichloro-2,2,2-trifluoroethane (HCFC-123) and 1,1-dichloro-1-fluoroethane (HCFC-141b) as blowing agents for the production of polyurethane foams. However, HCFCs also have some ozone-depletion potential. There is therefore mounting pressure to find substitutes for the HCFCs as well as the CFCs.
Alternative blowing agents which are currently considered promising because they contain no ozone-depleting chlorine are fluorocarbons (FCs) and partially fluorinated hydrocarbons (HFCs). The use of 1,1,1,4,4,4-hexafluorobutane as a blowing agent is disclosed in Lamberts, xe2x80x9c1,1,1,4,4,4-hexafluorobutane, a New Non-Ozone-Depleting Blowing Agent for Rigid PUR Foamsxe2x80x9d, Polyurethanes World Congress 1991 (September 24-26), pages 734-739. U.S. Pat. No. 4,972,002 teaches that low boiling fluorinated compounds such as fluorinated hydrocarbons, perfluorinated hydrocarbons, sulfur hexafluoride and mixtures thereof are useful as blowing agents for the production of polyisocyanate polyaddition foam products.
U.S. Pat. No. 4,898,893 teaches that a blend of a liquid hydrocarbon and halogenated hydrocarbon is useful as a blowing agent for the production of isocyanurate foams.
The use of mixtures of a chlorofluorocarbon having a boiling point between 74 and 120xc2x0 F. and an alkyl alkanoate having a molecular weight of no more than 88 as a blowing agent for foams is disclosed in U.S. Pat. No. 4,960,804. HCFC-123 and HCFC-141b are among the chlorofluorocarbons disclosed therein.
U.S. Pat. No. 5,035,833 discloses the use of a mixture of dichlorotrifluoroethane and at least one paraffin having 5 or 6 carbon atoms as blowing agents useful for the production of rigid polyurethane foams.
U.S. Pat. No. 5,096,933 discloses a process for the production of rigid polyurethane foams in which cyclopentane, cyclohexane or cyclopentane and cyclohexane, optionally in combination with a low boiling compound (i.e., boiling point less than 35xc2x0 C.) having no more than 4 carbon atoms which is homogeneously miscible with cyclopentane and/or cyclohexane is used.
U.S. Pat. No. 5,290,823 teaches the production of rigid polyurethane foams using a blowing agent mixture which includes highly fluorinated or perfluorinated organic compounds, cyclopentane and optionally other aliphatic or cycloaliphatic hydrocarbons having 4 to 8 carbon atoms.
U.S. Pat. No. 5,318,996 discloses the production of rigid polyurethane foams with a mixture of blowing agents which mixture includes water, HCFC-22 or HCFC-141b and a perfluorinated hydrocarbon having from 4 to 8 carbon atoms.
Mixtures and azeotropes of HCFCs and various compounds and azeotropes of organic compounds which may be used in combination with HCFCs have also been described in the prior art as being useful blowing agents for the production of foams.
U.S. Pat. No. 4,828,751 teaches solvent compositions for cleaning silicon wafers which solvent compositions include a perhalogenated haloalkylhydrocarbon containing from 5 to 12 carbon atoms and a partially fluorinated alcohol.
U.S. Pat. No. 4,900,365, for example, teaches that azeotropes of a dichlorotrifluoroethane and isopentane are useful in the production of polyurethane foams.
U.S. Pat. No. 5,106,527 discloses the use of azeotropes of 2-methyl butane and 1,1-dichloro-1-fluoroethane as blowing agents for the production of rigid, closed cell foams.
The azeotropic mixtures taught in U.S. Pat. No. 5,166,182 must have boiling points below 50xc2x0 C. These azeotropic mixtures are formed from organic compounds having surface active properties that enable the blended azeotropic mixture to become miscible with polymer resins. Examples of the organic compounds described as being useful in the production of such azeotropes include: n-pentane, acetone, methyl alcohol, methyl formate, ethyl formate, ethyl alcohol, 2-methyl butane, nitromethane, cyclopentane, 2,3-dimethyl butane, 2,2-dimethyl butane and dimethyl sulfide. These azeotropes may be used in combination with fluorocarbons but an azeotrope in which a fluorocarbon is one of the components is not taught or suggested.
U.S. Pat. No. 5,227,088 discloses azeotrope-like compositions which are made up of 1-chloro-3,3,3-trifluoropropane and a hydrocarbon containing five or six carbon atoms.
U.S. Pat. No. 5,283,003 discloses a blowing agent which is made up of at least one five-carbon member hydrocarbon, a chlorinated alkane and methyl formate. Methylene chloride is the preferred chlorinated alkane.
Azeotropic mixtures in which HCFCs are included are also known to be useful as cleaning solvents. U.S. Pat. No. 4,055,507, for example, discloses an azeotropic mixture of 1,2-dichloro-1,1-difluoroethane and 3-methylpentane which is taught to be useful as such a solvent. U.S. Pat. No. 5,302,212 teaches that an azeotrope of (perfluoroalkyl) ethylene and methanol may be used to clean a solid surface. Japanese 1,141,995 discloses an azeotropic mixture of 67 to 87% by weight of HCFC-123 and 13 to 33% by weight of 2-methyl butane which is useful as a cleaning solvent. Japanese 1,141,996 discloses an azeotropic mixture of HCFC-141b and n-pentane or 2-methyl butane or 2,2-dimethyl butane which is also taught to be useful as a cleaning solvent.
The use of azeotropes formed from perfluorohexane and a hydrocarbon having 5 carbon atoms as a blowing agent or a cleaning solvent has not, however, been described in the prior art.
It is an object of the present invention to provide novel azeotropic compositions.
It is a further object of the present invention to provide an azeotropic composition which contains no chlorine and therefore has an ozone depletion potential of zero.
It is also an object of the present invention to provide a process for the production of urethane foams in which no chlorine-containing blowing agent is employed.
It is another object of the present invention to provide polyurethane foams having good physical properties which foams are produced without the use of a chlorine containing blowing agent.
These and other objects which will be apparent to those skilled in the art are accomplished with the azeotropic compositions of the present invention. These azeotropic compositions are made up of (a) perfluoro-hexane and (b) one compound selected from (1) about 36 to about 74% by weight 2-methyl butane (i.e., from about 73 to about 93 mole %) or (2) about 28 to about 53% by weight (from about 65 to about 84 mole %) n-pentane, in which the sum of the weight percent of (a) and weight percent of (b), and the sum of the mole percent of (a) and mol percent of (b), respectively, is approximately 100 percent. These azeotropic compositions are included in a foam-forming mixture which includes an isocyanate and isocyanate-reactive material. The foams made with these azeotropic compositions are characterized by good physical properties.